This invention relates to a process for the preparation of quinacridone pigment compositions in the presence of mixtures of certain sulfonyl-containing derivatives of 2,5-dianilinoterephthalic acid.
Processes for the preparation of quinacridone are known. E.g., S. S. Labana and L. L. Labana, xe2x80x9cQuinacridonesxe2x80x9d in Chemical Review, 67, 1-18 (1967); W. Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York: VCH Publishers, Inc., 1997), pages 454-459; and U.S. Pat. Nos. 3,157,659, 3,256,285, and 3,317,539. The quinacridones thus obtained, known as crude quinacridones, are generally unsuitable for use as pigments and must undergo one or more additional finishing steps to modify the particle size, particle shape, or crystal structure to achieve pigmentary quality. For example, in a preferred method for preparing quinacridones, certain 2,5-dianilinoterephthalic acid precursors are thermally ring closed in the presence of polyphosphoric acid. E.g., U.S. Pat. No. 3,257,405. After ring closure is complete, the melt is drowned by pouring into a liquid in which the quinacridone is insoluble, usually water and/or an alcohol, after which the resultant crystalline pigment is typically further conditioned by solvent treatment and/or milling.
The addition of certain quinacridone derivatives or their precursors to the ring-closure step has been reported to enhance the coloristic and rheological properties of quinacridone pigments. For example, U.S. Pat. No. 5,368,641 discloses the use of various quinacridone derivatives in the manufacture of 2,9-dimethylquinacridone, U.S. Pat. No. 5,457,203 describes the use of quinacridone derivatives during the oxidation of dihydroquinacridone (prepared from 2,5-dianilino-3,6-dihydroterephthalic acid) to quinacridone, and U.S. Pat. Nos. 5,683,502 and 5,713,999 disclose the manufacture of quinacridone pigments in the presence of compounds other than quinacridones.
U.S. Pat. No. 5,755,873 describes the preparation of quinacridone pigments by ring closure of the corresponding dianilinoterephthalic acid precursors in the presence of various substituted dianilinoterephthalic acid derivatives, including 2,5-di(sulfamoylanilino)terephthalic acid. Although the resultant quinacridone pigment compositions typically exhibit improved coloristic and rheological properties, the quinacridone derivative that forms when using 2,5-di(sulfamoylanilino)terephthalic acid has an undesirable tendency to bleed from the resultant pigment preparations, which can adversely affect their use.
It has now been found that quinacridone pigment compositions exhibiting an advantageous combination of coloristic and rheological properties without excessive bleeding associated with 2,5-di(sulfamoylanilino)terephthalic acid can be obtained by using reduced quantities of 2,5-di(sulfamoylanilino)terephthalic acid in combination with other sulfonyl-containing derivatives of 2,5-dianilinoterephthalic acid during quinacridone synthesis.
The present invention relates to a process for the preparation of quinacridone pigment compositions comprising
(a) heating, at a temperature of about 80xc2x0 C. to about 145xc2x0 C. (preferably 95xc2x0 C. to 130xc2x0 C.) (preferably for about one to about 24 hours), a reaction mixture comprising
(i) 2,5-dianilinoterephthalic acid or 2,5-dianilino-6,13-dihydroterephthalic acid or a derivative of 2,5-dianilinoterephthalic acid or 2,5-dianilino-6,13-dihydroterephthalic acid having one or more substituents other than sulfonyl groups in at least one aniline ring, a salt or ester thereof, or a mixture thereof,
(ii) about 0.1 to about 5 percent by weight (preferably 1 to 3 percent by weight), based on component (a)(i), of a 2,5-di(sulfamoylanilino)terephthalic acid having the formula (I) 
xe2x80x83and/or a 2,5-di(sulfamoylanilino)-6,13-dihydroterephthalic acid having the formula (Ixe2x80x2) 
xe2x80x83wherein W1 and W2 are independently hydrogen, halogen,
C1-C6 alkyl, or C1-C6 alkoxy,
(iii) about 0.1 to about 15 percent by weight (preferably 5 to 10 percent by weight), based on component (a)(i), of one or more sulfonyl-containing derivatives of 2,5-dianilinoterephthalic acid having the formula (II) 
xe2x80x83and/or one or more sulfonyl-containing derivatives of 2,5-dianilino-6,13-dihydroterephthalic acid having the formula (IIxe2x80x2) 
xe2x80x83wherein
X1 and X2 are independently ORa or NRbRc,
Y1 and Y2 are independently hydrogen, halogen, C1-C6 alkyl, or C1-C6 alkoxy,
R1 and R2 are independently hydrogen, a metal, an ammonium ion, or C1-C12 alkyl,
Ra is hydrogen, a metal, an ammonium ion, or C1-C12 alkyl,
Rb is hydrogen, C1-C12 alkyl or substituted C1-C12 alkyl, C5-C7 cycloalkyl or substituted C5-C7 cycloalkyl, C6-C10 aryl, heteroaryl having five or six ring atoms (in which at least one such ring atom is N, O, S, or a combination thereof, and which is optionally fused to one or more additional aromatic rings), or C7-C16 aralkyl,
Rc is hydrogen, C1-C12 alkyl or substituted C1-C12 alkyl, C5-C7 cycloalkyl or substituted C5-C7 cycloalkyl, or C7-C16 aralkyl, or Rb and Rc together with the nitrogen atom form a heterocycle having 5 to 7 ring atoms, and
xe2x80x83m and n are independently from 0 to 3, with the provisos that
(1) at least one of m or n is not 0 (preferably where both m and n are 1),
(2) if X1 and X2 are both NH2, then either (A) at least one of Y1 or Y2 must be halogen, C1-C6 alkyl, or C1-C6 alkoxy or (B) Y1 must be different from W1 and/or Y2 must be different from W2 (i.e., so that component (iii) is always different from component (ii)), and
(3) if any one or more of components (a)(i), (a)(ii), or (a)(iii) is a 2,5-dianilino-6,13-dihydroterephthalic acid or any derivative thereof, reaction step (a) additionally comprises an oxidation step (which converts the initially formed dihydroquinacridone intermediate to the corresponding quinacridone),
(iv) about 3 to about 20 parts by weight (preferably 3 to 10 parts by weight), per part of component (a)(i), of a dehydrating agent (preferably polyphosphoric acid), and
(v) 0 to about 20 parts by weight, per part of component (a)(i), of a solvent;
(b) drowning the reaction mixture from step (a) by adding said reaction mixture to about 3 to about 15 parts by weight (preferably 5 to 10 parts by weight), per part of component (a)(i), of a liquid in which the quinacridone pigment composition is substantially insoluble;
(c) isolating the quinacridone pigment composition;
(d) optionally, conditioning the quinacridone pigment composition; and
(e) optionally, blending (preferably dry blending) the resultant quinacridone pigment composition with one or more pigment derivatives (preferably quinacridone derivatives).
Quinacridone pigments (by which is meant unsubstituted quinacridone, quinacridone derivatives, and solid solutions thereof) are prepared according to the invention by first ring-closing 2,5-dianilinoterephthalic acid precursors, including known aniline-substituted derivatives thereof, as well as their metal or amine salts or esters, by heating the 2,5-dianilinoterephthalic acid precursors in the presence of a dehydrating agent (preferably polyphosphoric acid) and a sulfonyl-containing derivative of 2,5-dianilinoterephthalic acid according to the invention or, less preferably, by thermally inducing ring closure in a high-boiling solvent in the presence of a sulfonyl-containing derivative of 2,5-dianilinoterephthalic acid according to the invention. The quinacridone-containing reaction mixture is then drowned and the resultant quinacridone pigment composition is isolated by known methods. Although generally not necessary, the resultant quinacridone pigment composition can also be subjected to additional conditioning steps to improve pigmentary properties and, if desired, blended with various additives.
Ring-closure step (a) is carried out in a dehydrating agent, particularly a strong acid such as polyphosphoric acid, acidic esters of polyphosphoric acid, or sulfuric acid. E.g., U.S. Pat. No. 4,758,665; and S. S. Labana and L. L. Labana, xe2x80x9cQuinacridonesxe2x80x9d in Chemical Reviews, 67, 1-18 (1967); and W. Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York:VCH Publishers, Inc., 1997), pages 457-458. Polyphosphoric acid having a phosphate content equivalent to about 110-120% H3PO4 is particularly preferred. When using polyphosphoric acid, the weight ratio of polyphosphoric acid to the total amount of terephthalic acid precursors, including the amount of sulfonyl-containing derivatives, is typically about 3:1 to about 10:1 (preferably 4:1 to 8:1). This method does not require solvents (other than the dehydrating agents themselves). The reaction mixture of step (a) is heated at a temperature of about 80xc2x0 C. to about 145xc2x0 C. (preferably 95xc2x0 C. to 130xc2x0 C.), preferably for about 1 to about 24 hours (more preferably for 1 to 12 hours).
It is sometimes preferable to use a 2,5-dianilino-6,13-dihydroterephthalic acid (preferably as a C1-C6 alkyl ester) or a derivative thereof as a starting material for any of the components (a)(i), (a)(ii), or (a)(iii) in the ring-closure reaction, after which the resultant dihydroquinacridone must be oxidized by known methods (for example, using aromatic nitro compounds, chloroanil, anthraquinone-2-sulfonic acid or a salt thereof, anthraquinone-2,7-disulfonic acid or a salt thereof, air or other oxygen-containing gases, halogens, or electrolytic oxidation) to form the corresponding quinacridones, which are collected by known methods. When using this method, dehydration is typically carried out in a solvent, preferably a high-boiling solvent or solvent mixture such as diphenyl ether/diphenyl. E.g., S. S. Labana and L. L. Labana, xe2x80x9cQuinacridonesxe2x80x9d in Chemical Review, 67, 1-18 (1967) (see pages 4-5), and W. Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York:VCH Publishers, Inc., 1997), pages 456-457. The present invention is also directed to this variant of quinacridone synthesis. It is, of course, possible to use mixtures of 2,5-dianilino-6,13-dihydroterephthalic acids and/or derivatives thereof to obtain quinacridone solid solutions.
The process of the invention can be used to prepare unsubstituted quinacridone or ring-substituted quinacridone derivatives, depending on whether the ring closure is carried out using unsubstituted 2,5-dianilinoterephthalic acid or 2,5-dianilino-6,13-dihydroterephthalic acid or a derivative thereof having one or more substituents in at least one of the two aniline rings. Although essentially any 2,5-dianilinoterephthalic or 2,5-dianilino-6,13-dihydroterephthalic acid derivatives known in the art can be used, particularly preferred 2,5-dianilinoterephthalic and or 2,5-dianilino-6,13-dihydroterephthalic acid derivatives are those in which both of the aniline moieties are substituted (typically with the same substituent) at the para position with groups such as halogen (preferably chlorine), C1-C6 alkyl (preferably methyl), and C1-C6 alkoxy (preferably methoxy). It is also possible to use derivatives of 2,5-dianilinoterephthalic acid or 2,5-dianilino-6,13-dihydroterephthalic acid in which the aniline moieties are substituted in the ortho or meta positions. The corresponding metal or amine salts (preferably alkali or alkaline earth metal salts) or esters (preferably alkyl esters) of each of the above compounds can, of course, also be used. Examples of particularly suitable 2,5-dianilinoterephthalic acid derivatives are 2,5-di(4-chloroanilino)terephthalic acid, 2,5-di(4-methylanilino)terephthalic acid, and 2,5-di(4-methoxyanilino)terephthalic acid.
It is also possible to use mixtures containing 2,5-dianilinoterephthalic acid or 2,5-dianilino-6,13-dihydroterephthalic acid and one or more derivatives thereof or mixtures containing two or more 2,5-dianilinoterephthalic or 2,5-dianilino-6,13-dihydroterephthalic acid derivatives. The use of such mixtures provides a particularly advantageous method for obtaining quinacridone solid solutions. Mixtures containing 2,5-dianilinoterephthalic acid or 2,5-dianilino-6,13-dihydroterephthalic acid or a derivative thereof in combination with a fully formed quinacridone pigment (generally in crude form) can also be used.
A critical feature of the invention is the inclusion of mixtures of small quantities of the 2,5-di(sulfamoylanilino)terephthalic acid compounds (a)(ii) in conjunction with other sulfonyl-containing 2,5-dianilinoterephthalic acid derivatives (a)(iii) during the ring-closure reaction used to prepare the quinacridone pigment composition. The compounds can be added at essentially any point during or before ring-closure step (a). Although additive precursors (a)(ii) and (a)(iii) can themselves produce highly colored quinacridone derivatives, the utility of the additive precursors is not dependent on the production of quinacridone derivatives that exhibit good pigmentary properties.
Suitable 2,5-di(sulfamoylanilino)terephthalic acid derivatives have the following formula (I) 
in which W1 and W2 can be hydrogen, halogen, C1-C6 alkyl, or C1-C6 alkoxy. A particularly preferred precursor is unsubstituted 2,5-di(sulfamoylanilino)terephthalic acid, in which W1 and W2 are both hydrogen, as represented by formula (Ia) 
Analogous 2,5-di(sulfamoylanilino)-6,13-dihydroterephthalic acid derivatives of formula (Ixe2x80x2) are also suitable, particularly when using 2,5-dianilino-6,13-dihydroterephthalic acids or derivatives thereof as starting materials (a)(i) and (a)(iii). The sulfonyl-containing dihydroquinacridones that form during ring closure can be oxidized to the corresponding sulfonyl-containing quinacridones under the same conditions used to oxidize the dihydroquinacridone intermediates of the other components.
Suitable sulfonyl-containing derivatives of 2,5-dianilinoterephthalic acid have the following formula (II) 
in which X1 and X2 can independently be OH (i.e., free sulfonic acid groups), Oxe2x88x92cation+(i.e., salts of metals or various ammonium ions), O-alkyl (i.e., sulfonic acid alkyl esters), or NRbRc (i.e., various sulfon-amides in which each Rb can independently be hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl, or aralkyl and each Rc can independently be hydrogen or an optionally substituted alkyl, cycloalkyl, or aralkyl or in which Rb and Rc together with the nitrogen atom can form a heterocycle having 5 to 7 ring atoms); Y1 and Y2 can independently be hydrogen, halogen, alkyl, or alkoxy; and m and n can be from 0 to 3 as long as at least one of m or n is not zero. In preferred embodiments, the Y1 and Y2 groups are identical and all X1 and X2 groups are identical. However, to assure that component (a)(iii) is always different from component (a)(ii), X1 and X2 can both be NH2 only if at least one of Y1 or Y2 is halogen, C1-C6 alkyl, or C1-C6 alkoxy or if Y1 is different from W1 and/or Y2 is different from W2.
Analogous sulfonyl-containing derivatives of 2,5-dianilino-6,13-dihydroterephthalic acid derivatives of formula (IIxe2x80x2) are also suitable, particularly when using 2,5-dianilino-6,13-dihydroterephthalic acids or derivatives thereof as starting materials (a)(i) and (a)(ii). The sulfonyl-containing dihydroquinacridones that form during ring closure can be oxidized to the corresponding sulfonyl-containing quinacridones under the same conditions used to oxidize the dihydroquinacridone intermediates of the other components.
As used herein, the term xe2x80x9cC1-C12 alkylxe2x80x9d refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 12 carbon atoms. Examples of C1-C12 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the isomeric forms thereof. The C1-C12 alkyl groups can also be substituted, for example, with one or more C1-C6 alkoxy, C1-C6 alkylthio, or halogen groups. The term xe2x80x9cC1-C6 alkoxyxe2x80x9d refers to straight or branched chain alkyl oxy groups having from 1 to 6 carbon atoms. Examples of C1-C6 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the isomeric forms thereof. The term xe2x80x9cC1-C6 alkylthioxe2x80x9d refers to analogous groups in which a sulfur atom replaces the oxygen atom. The term xe2x80x9cC5-C7 cycloalkylxe2x80x9d refers to cycloaliphatic hydrocarbon groups having from 5 to 7 carbon atoms. Examples of C5-C7 cycloalkyl are cyclopentyl, cyclohexyl, and cycloheptyl. The C5-C7 cycloalkyl groups can also be substituted, for example, with one or more C1-C6 alkoxy, C1-C6 alkylthio, or halogen groups. The term xe2x80x9cC6-C10 arylxe2x80x9d refers to phenyl and 1- or 2-naphthyl, as well as to phenyl and naphthyl groups substituted with alkyl, alkoxy, halogen, cyano, and nitro. The term xe2x80x9cheteroarylxe2x80x9d refers to five- and six-membered aromatic groups in which at least one ring atom is N, O, S, or a combination thereof, and which can optionally be fused to one or more additional aromatic rings. Such heteroaryl groups are attached to the sulfonamide nitrogen atom at a ring carbon atom. Examples of heteroaryl are pyrrolyl, imidazolyl, pyrazolyl, furanyl, thiophenyl, isothiazolyl, isoxazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like. The term xe2x80x9cC7-C16 aralkylxe2x80x9d refers to C1-C6 alkyl substituted with C6-C10 aryl such that the total number of carbon atoms is from 7 to 16. Examples of C7-C16 aralkyl are benzyl, phenethyl, and naphthylmethyl. The term xe2x80x9cheterocyclexe2x80x9d, as used to describe compounds in which NRbRc is a heterocycle having 5 to 7 ring atoms, includes groups in which Rb and Rc together are linear C4-C6 alkylene, alkenylene, alkadienylene, or alkatrienylene groups having one or more substituents (such as alkyl, alkoxy, or halogen) and the nitrogen atom is always tertiary rather than quaternary. Suitable heterocycles also include groups in which one or more of the ring carbon atoms is replaced with N, O, or S (the maximum number of double bonds in the ring being limited, of course, to the number giving chemically reasonable heterocyclic groups). Examples of suitable heterocycles include pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrazolinyl, piperidinyl, piperazinyl, morpholinyl, and the like. Examples of halogen are fluorine, chlorine, bromine, and iodine.
Although it is possible to use sulfonyl-containing 2,5-dianilinoterephthalic or 2,5-dianilino-6,13-dihydroterephthalic acid derivatives containing one or more substituents in addition to the sulfonyl groups, including, for example, halogen (preferably chlorine), C1-C6 alkyl (preferably methyl), and C1-C6 alkoxy (preferably methoxy), the preferred 2,5-dianilinoterephthalic acid derivatives contain no substituents other than the sulfonyl groups. Particularly preferred 2,5-dianilinoterephthalic acid derivatives are xe2x80x9cdisulfonylxe2x80x9d compounds of formula (IIa) 
in which X1 and X2 are defined as above, except that X1 and X2 cannot both be NH2.
Among the preferred sulfonyl-containing 2,5-dianilinoterephthalic acid derivatives are sulfonic acids (or salts thereof) having the following formula (IIb) 
in which Ra is defined as above. The preferred compounds of formula (IIb) are the free sulfonic acids (i.e., in which Ra is hydrogen), but it is also possible to use the corresponding metal or ammonium salts. Suitable metals include alkali metals (such as lithium, sodium, and potassium), alkaline earth metals (such as magnesium, calcium, and barium), aluminum, transition metals and other heavy metals (such as nickel, iron, cobalt, manganese, copper, and tin), the polyvalent metals being used in stoichiometrically appropriate amounts (i.e., 1/k moles of a k-valent metal per mole of oxygen). Suitable ammonium cations include NH4+ and various N-alkyl, N-aryl, and/or N-aralkyl-substituted derivatives thereof. Although the strongly acidic conditions typically used for ring closure may convert such salts to the corresponding free sulfonic acids, it may nevertheless be advantageous to add the sulfonyl-containing 2,5-dianilinoterephthalic acid derivatives in salt form.
Particularly preferred sulfonyl-containing 2,5-dianilinoterephthalic acid derivatives include sulfonamides having the following formula (IIc) 
in which each Rb is independently hydrogen, alkyl or substituted alkyl, cycloalkyl or substituted cycloalkyl, aryl, heteroaryl, or aralkyl and each Rc is independently alkyl or substituted alkyl, cycloalkyl or substituted cycloalkyl, or aralkyl or, somewhat less preferably, in which Rb and Rc together with the nitrogen atom form a heterocycle having 5 to 7 ring atoms. Preferred compounds of formula (IIc) are those in which Rb and Rc are both alkyl or in which Rb is alkyl, aryl, or heteroaryl and Rc is hydrogen.
Although the use of strongly acidic dehydrating agents (especially polyphosphoric acid) at elevated temperatures might be expected to convert many if not all of the sulfonamide groups of sulfonamide-containing compounds (such as those of formula (IIc), as well as formula (I)) to the corresponding free sulfonic acids, it nevertheless appears to be advantageous to use sulfonamides such as those of formula (IIc) instead of the corresponding free acids, salts, or esters.
It is possible, but not necessary, to add various fully formed quinacridone derivatives, particularly sulfonyl-containing quinacridone products prepared from sulfonyl-containing 2,5-dianilinoterephthalic acid derivatives such as used in the invention, to the ring-closure step.
After ring-closure step (a) (including any necessary oxidation) is completed, the quinacridone pigment composition is precipitated (i.e., xe2x80x9cdrownedxe2x80x9d) in step (b) by adding the strongly acidic melt to a liquid in which the quinacridone pigment composition is substantially insoluble, preferably water, a water-miscible solvent (such as methanol, or other lower aliphatic alcohols), or mixtures thereof. Although it is possible to add the drowning liquid to the acidic melt (e.g., U.S. Pat. No. 3,265,699), the present invention is preferably carried out by adding the acidic melt to the solvent (compare U.S. Pat. No. 4,100,162).
Suitable drowning liquids include water and/or water-miscible organic liquids; including, for example, lower aliphatic alcohols, such as methanol; ketones and ketoalcohols, such as acetone, methyl ethyl ketone, and diacetone alcohol; amides, such as dimethylformamide and dimethylacetamide; ethers, such as tetrahydrofuran and dioxane; alkylene glycols and triols, such as ethylene glycol and glycerol; and other such organic liquids known in the art. Other organic liquids can be used but are generally less preferred.
The temperature of the drowning liquid is usually between about 5xc2x0 C. and about 65xc2x0 C. In general, lower drown temperatures give pigments having smaller particle sizes. However, because process cycle time is also very important (because of manufacturing cost), a shorter drowning time is preferred. The presence of pigment derivatives (a)(ii) and (a)(iii), which act in part as particle growth inhibitors, allows the solvent temperature to rise during the drowning process, thus shortening the time without excessive particle size growth.
The drowned pigment composition is then isolated in step (c) using methods known in the art, such as filtration, and then dried if desired. Other collection methods known in the art, such as centrifugation, microfiltration, or even simple decantation, are also suitable.
Although generally not necessary, the crystalline pigment composition obtained in step (c) can be conditioned in an optional step (d) using methods known in the art, such as solvent treatment or milling in combination with solvent treatment. Suitable milling methods include dry-milling methods such as sand-milling, ball-milling, and the like, with or without additives, or wet-milling methods such as salt-kneading, bead-milling, and the like in water or organic solvents, with or without additives.
Tinctorial strength and transparency of the pigment composition can also be affected by solvent treatment carried out by heating a dispersion of the pigment composition, often in the presence of additives, in a suitable solvent. Suitable solvents include organic solvents, such as alcohols, esters, ketones, and aliphatic and aromatic hydrocarbons and derivatives thereof, and inorganic solvents, such as water. Suitable additives include compositions that lessen or avoid flocculation, increase pigment dispersion stability, and reduce coating viscosity, such as polymeric dispersants (or surfactants). E.g., U.S. Pat. Nos. 4,455,173; 4,758,665; 4,844,742; 4,895,948; and, 4,895,949.
During or after the optional conditioning step it is possible, but generally not necessary, to use various other optional ingredients that provide improved properties. Examples of such optional ingredients include fatty acids having at least 12 carbon atoms, such as stearic acid or behenic acid, or corresponding amides, esters, or salts, such as magnesium stearate, zinc stearate, aluminum stearate, or magnesium behenate; quaternary ammonium compounds, such as tri[(C1-C4 alkyl)-benzyl]ammonium salts; plasticizers, such as epoxidized soya bean oil; waxes, such as polyethylene wax; resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin; C12-C18-paraffin-disulfonic acids; alkylphenols; alcohols, such as stearyl alcohol; amines, such as laurylamine or stearylamine; and aliphatic 1,2-diols, such as dodecane-1,2-diol. Such additives can be incorporated in amounts ranging from about 0.05 to 20% by weight (preferably 1 to 10% by weight), based on the amount of pigment composition.
After the pigment composition has been isolated and optionally conditioned, the pigment composition can be blended (preferably by dry blending) with one or more pigment derivatives known in the art. Suitable pigment derivatives for step (e) include quinacridone derivatives, particularly known quinacridone sulfonic acids and sulfonamides and quinacridone derivatives containing other substituents (such as substituents containing phthalimide or heteroaromatic groups).
Pigment compositions prepared according to the invention characteristically exhibit deep (dark), bright, transparent masstones, along with bright, blue metallics, and blue tints, and sometimes exhibit improved rheological properties, all of which are highly desirable characteristics of quinacridone pigments, especially when used for automotive applications.
Because of their advantageous properties, the quinacridone pigment compositions prepared according to the present invention are suitable for many different pigment applications. For example, pigment compositions prepared according to the invention can be used as the colorant (or as one of two or more colorants) for very fast pigmented systems, such as mixtures with other materials, pigment formulations, paints, printing ink, colored paper, or colored macromolecular materials. The term xe2x80x9cmixture with other materialsxe2x80x9d can be understood to include, for example, mixtures with inorganic white pigments, such as titanium dioxide (rutile) or cement, or other inorganic pigments. Examples of pigment formulations include flushed pastes with organic liquids or pastes and dispersions with water, dispersants, and if appropriate, preservatives. Examples of paints in which pigment compositions of this invention can be used include, for example, physically or oxidatively drying lacquers, stoving enamels, reactive paints, two-component paints, solvent- or water-based paints, emulsion paints for weatherproof coatings, and distempers. Printing inks include those known for use in paper, textile, and tinplate printing. Macromolecular substances include those of a natural origin, such as rubber; those obtained by chemical modification, such as acetyl cellulose, cellulose butyrate, or viscose; or those produced synthetically, such as polymers, polyaddition products, and polycondensates. Examples of synthetically produced macromolecular substances include plastic materials, such as polyvinyl chloride, polyvinyl acetate, and polyvinyl propionate; polyolefins, such as polyethylene and polypropylene; high molecular weight polyamides: polymers and copolymers of acrylates, methacrylates, acrylonitrile, acrylamide, butadiene, or styrene; polyurethanes; and polycarbonates. The materials pigmented with the quinacridone pigments of the present invention can have any desired shape or form.
Pigment compositions prepared according to this invention are highly water-resistant, oil-resistant, acid-resistant, lime-resistant, alkali-resistant, solvent-resistant, fast to over-lacquering, fast to over-spraying, fast to sublimation, heat-resistant, and resistant to vulcanizing, yet give a very good tinctorial yield and are dispersible.
The following examples further illustrate details for the process of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all percentages are percentages by weight.